US5070123A - Method for improving the storage stability of polymer modified asphalt - Google Patents
Method for improving the storage stability of polymer modified asphalt Download PDFInfo
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- US5070123A US5070123A US07/397,215 US39721589A US5070123A US 5070123 A US5070123 A US 5070123A US 39721589 A US39721589 A US 39721589A US 5070123 A US5070123 A US 5070123A
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- polymer
- asphalt
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C3/00—Working-up pitch, asphalt, bitumen
- C10C3/02—Working-up pitch, asphalt, bitumen by chemical means reaction
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
Definitions
- the present invention relates to a composition and method for improving the storage stability of polymer modified asphalts.
- Asphalt is a bituminous material resulting from the distillation of crude oil.
- asphalt is derived from the bottoms of a vacuum distillation tower and has an atmospheric boiling point of at least 380° C. Because it is hydrophobic and has good adhesiveness and weatherability, asphalt has been used widely as a binder in paving materials and as a coating for roofing shingles.
- polymeric materials have been added to asphalt to enhance its rheological properties, i.e., to improve its creep resistance above about 20° C.
- Polymer modified asphalts must also have good phase compatibility between the asphalt and polymer, and be storage stable at high temperatures for ease of handling and application. Compatibility between the polymer and asphalt is very important to ensure that the properties of both are transferred to the finished product for good long term performance. Poor storage stability will render the polymer modified asphalt unsuitable for use in paving binder applications, roofing applications, and other industrial specialty products. Accordingly, various methods have been suggested for maintaining storage stability.
- One method requires continuous mixing of the asphalt/polymer mixture to avoid phase separation (See, for example, U.S. Pat. Nos. 4,240,946 and 4,314,921, which require high shear mixing to obtain physical dispersion of a polyolefin in bitumen. See also Transportation and Road Research Laboratory Report 1101 by J. H. Denning et. al., Highways and Structures Department, Crowthorne, Berkshire, England (1983)).
- Another method discloses adding one or more dispersants to a polyethylene modified asphalt to avoid phase separation (See Jew et al., Journal of Applied Polymer Science, 31, pp.2685-2704 (1986)).
- composition of the asphalt is tailored to ensure compatibility with the polymer used or the polymer is selected to be compatible with the asphalt (See U.S. Serial Nos. 073,813 filed June 15, 1987 and 134,954 filed Dec. 18, 1987).
- polymer modified asphalt is stabilized by the addition of an acid after the polymer has been added to the asphalt (See, for example, German patent DE 22 55 173 C3 which discloses stabilizing mixtures of asphalt and styrenic thermoplastic elastomers (styrene-butadiene-styrene) by adding small amounts of 85% o-phosphoric acid or 36% hydrochloric acid to the asphalt/SBS mixture).
- This invention relates to a composition and method for improving the storage stability of polymer modified asphalts. More specifically, the storage stability of an asphalt that contains greater than 1.0 wt.% of a polymer can be enhanced if the asphalt is contacted with an inorganic acid prior to adding the polymer. The resulting acid treated polymer modified product will have enhanced storage stability relative to that obtained had the acid been added with or after the polymer.
- the asphalt used in this invention may be obtained from a variety of sources including straight-run vacuum residue; mixtures of vacuum residue with diluents such as vacuum tower wash oil, paraffin distillate, aromatic and naphthenic oils, and mixtures thereof; oxidized vacuum residues or oxidized mixtures of vacuum residues and diluent oils; and the like.
- Other asphaltic materials such as coal tar pitch, rock asphalt, and naturally occurring asphalt may also be used.
- the asphalt will have an atmospheric boiling point of at least 380° C., more typically of at least 440° C., and an asphaltene content of between about 5 and about 30 wt.% as determined by ASTM D4124.
- the asphalt will typically comprise 85, preferably 90, wt.% or more of the acid treated polymer modified product (i.e., the final product).
- the asphalt will typically comprise 80, preferably 85, wt.% or more of the final product when it is used in roofing applications.
- An inorganic acid is then contacted with, or added to, the asphalt to form an acid treated asphalt.
- acid addition improves the temperature susceptibility of the asphalt and the stability of the acid treated polymer modified blend.
- the inorganic acid is added slowly to the asphalt to avoid foaming which may occur if all the acid were added at one time.
- the inorganic acid content of the asphalt is not critical, but normally should range between about 0.2 and about 5.0 wt.%, preferably between about 0.25 and about 3.0 wt.%, of the asphalt.
- the inorganic acid will preferably be selected from the group consisting of hydrochloric acid, phosphoric acid, phosphorus pentoxide, sulfuric acid, and mixtures thereof.
- the term "inorganic acid” is meant to include compounds that are capable of forming an inorganic acid when contacted with the asphalt (e.g., chlorinated paraffin wax and polyvinyl chloride release hydrochloric acid when contacted with hot asphalt). Hydrochloric acid, phosphoric acid, phosphorus pentoxide, and mixtures thereof are preferred inorganic acids, with phosphoric acid being particularly preferred.
- the polymer is then added to the acid treated asphalt to form an acid treated polymer modified asphalt that has enhanced storage stability relative to the storage stability obtained if the polymer were added prior to or concurrent with the inorganic acid.
- the asphalt must contain greater than 1.0 wt.% (preferably at least 1.5 wt.% and more preferably at least 2.0 wt.%) of the polymer for the storage stability to be enhanced by acid addition.
- polymer modified asphalts appear to be storage stable without acid addition.
- polymer modified asphalts are believed to become increasingly less stable as the polymer concentration in the asphalt increases above 1.0 wt.%.
- the upper limit on the amount of polymer in the asphalt is not critical and can range up to 15 wt.% or more based on weight percent of the acid treated asphalt, although amounts below 15 wt.% are preferred. Therefore, the amount of polymer in the asphalt will typically range from above 1.0 to about 15 wt.% based on weight of the acid treated asphalt. Preferably, the amount of polymer in the asphalt will range from about 1.5 to about 15 wt.% and more preferably from about 2.0 to about 15 wt.%.
- the acid treated polymer modified asphalt normally contains from about 4 to about 8 wt.% polymer. When used for roofing applications, the acid treated polymer modified asphalt normally contains from about 8 to about 15 wt.% polymer.
- Suitable polymers include both thermoplastics and thermosets, as defined by ASTM D 883-69 Standard Definitions of Terms Relating to Plastics, the disclosure of which is incorporated herein by reference.
- ASTM D 883-69 defines a thermoplastic as a polymer that can be repeatedly softened when heated and hardened when cooled.
- a thermoset is defined as a polymer that can be changed into a substantially infusible or insoluble product when cured by heat or by chemical means.
- thermoplastics examples include acetals (e.g., polymers and copolymers of formaldehyde), acrylics, acrylonitrile-butadiene-styrene plastics, cellulosics (such as cellulose acetate, propionate and acetate-butyrate), chlorinated polyethylene, fluorocarbons, nylon, polycarbonates, polyethylenes, polyphenylene oxides, polyphenylene sulfides, polypropylene, polystryene, polysulfone, polyvinyl acetates, polyvinyl alcohols, polyvinyl chlorides, polyvinylidine chloride, styrene-acrylonitrile plastics, saturated polyesters, and thermoplastic elastomers of all classes including urethanes, polyesters, styrenics and olefinics.
- acetals e.g., polymers and copolymers of formaldehyde
- acrylics acrylonitrile-
- thermoplastics are polyethylene, ethylene methacrylate, ethylene-propylene elastomer, ethylene-vinyl acetate, nylon, uncured ethylene-propylene-diene terpolymers, and uncured thermoplastic styrenic elastomers (e.g., styrene-butadiene-styrene block copolymers), with ethylene methacrylate, ethylene-vinyl acetate, or their mixtures being most preferred.
- styrenic elastomers e.g., styrene-butadiene-styrene block copolymers
- thermosets examples include amino resins (e.g., melamine-formaldehyde, urea-formaldehyde, and mixtures thereof), phenolics, polyimides, polyuretyanes, polysulfides, silicone rubbers, unsaturated polyesters, and vulcanized (i.e., cured) rubbers (e.g., natural rubbers and cured elastomers such as ethylene-propylene-diene terpolymers and styrene-butadiene-styrene block copolymers).
- Preferred thermosets are polyimides, polyurethanes, and vulcanized rubbers. Most preferred are polyurethanes, cured elastomers, or their mixtures.
- the conditions at which the acid and polymer are added to the asphalt are not critical and will vary with the particular asphalt and polymer used. However, the conditions will be within the ranges normally used for acid or polymer addition to asphalt.
- acid is normally added slowly to the asphalt (typically, over a period of from about 1 to about 3 hours) at a temperature of from about 150° C. to about 250° C., preferably from about 180° C. to about 210° C.
- the acid treated asphalt is mixed for an additional period of time (typically from about 0.5 to about 1 hour, although longer times could be used because no further reaction is likely to occur once all of the acid has been reacted or depleted).
- the polymer is then added to the acid treated asphalt at a temperature of from about 150° to about 300° C., preferably from about 175° to about 230° C. Typically, the polymer will be added over a period of from about 1.5 to about 3 hours to ensure adequate dispersal of the polymer. Although the polymer can be added over a longer period of time, it is important not to add the polymer over too short a period because the polymer could then melt and coalesce when contacted by the hot acid treated asphalt. This would slow dispersal of the polymer in the asphalt. Once polymer addition is complete, the acid treated polymer modified asphalt is mixed for an additional 0.5 to 1.5 hours or more.
- the asphalt may be mixed or blended with the acid and polymer in any number of ways that can readily be selected by one skilled in the art. Suitable means include external mixers, roll mills, internal mixers, Banbury mixers, screw extruders, augers, and the like. Normally, the mixing or blending during acid and polymer addition will be at ambient pressure.
- An oxygen-containing gas such as air
- the gas is not added before or during either step because it would tend to produce asphaltenes, which would have a detrimental effect on the storage stability of the final product.
- the acid treated polymer modified asphalt thus formed may be employed in essentially any application requiring asphalt-based products with superior storage stability.
- applications include adhesives, coatings, fabricated products, road and roofing applications, sealants, sound and vibration dampening products, water proofing membranes and the like.
- the final product is particularly well suited for use as a paving binder, particularly a binder in the load bearing course as well as the top or surface course of hot mix pavement structures.
- the storage stability of the acid treated polymer modified asphalts tested was measured by placing a 200 gram sample in a copper tube (10 inches high and 1 inch in diameter) and heating it to 160° C. for 5 days. Then the sample was removed from the tube and divided into top and bottom fractions. The viscosity of each fraction was measured at 135° C. and then used to calculate the ratio of the top to the bottom viscosity. A ratio of 1.0 is considered as optimum storage stability, with ratios above or below 1.0 representing mixtures that are increasingly less storage stable.
- Tests were performed on several samples of a 300/400 penetration straight-run asphalt obtained from vacuum distillation. Phosphoric acid (85 wt.%) and ethylene-vinyl acetate (EVA) polymer, each alone or in combination, were added to the samples. The temperature of the samples ranged between 190° and 200° C. at all times during the tests. The order and conditions of acid and polymer addition were varied as follows:
- Example 1 was repeated using styrene-butadiene-styrene as the polymer except that when the acid and polymer were added together, both were added over about a twenty minute period followed by reaction with the asphalt for about an additional two hours.
- the properties of the samples tested were determined and are summarized in Table 2.
- Example 3 Using the procedure of Example 1, tests were performed on samples of a 150/200 straight-run asphalt. In one sample, only polymer was added. In two other samples, HCl (or Chlorez 760, a chlorinated wax available from Dover Chemical Corp.) was added before addition of ethylene-vinyl acetate. The properties of the samples tested were determined and are shown in Table 3.
- Chlorez 760 and a different grade of ethylene-vinyl acetate were added to samples of a 100/200 penetration straight-run asphalt, the Chlorez 760 being added before the polymer.
- the properties of the samples tested were then determined and the results shown in Table 5.
- Example 2 Using the procedure of Example 1, hydrochloric acid (or Chlorez 760) and the ethylene-vinyl acetate of Example 1 were added to samples of a 100/200 penetration straight-run asphalt, with the acid (or Chlorez 760) being added first. The properties of the samples tested were then determined and the results shown in Table 6.
- Example 1 was repeated at different concentrations of phosphoric acid and ethylene-vinyl acetate in which the acid was added to the asphalt before the polymer. The results obtained are shown in Table 7.
Abstract
This invention relates to a composition and method for improving the storage stability of polymer modified asphalts. More specifically, the storage stability of an asphalt which contains greater than 1.0 wt. % polymer can be improved by adding the polymer to an asphalt which has previously been reacted with an inorganic acid. The storage stable acid treated polymer modified asphalt thus produced is particularly well suited for use as a binder in paving materials and as a coating or saturant for roofing shingles.
Description
This is a continuation of U.S. Ser. No. 237,028, filed Aug. 29, 1988 now abandoned.
1. Field of the Invention
The present invention relates to a composition and method for improving the storage stability of polymer modified asphalts.
2. Discussion of Related Art
Asphalt is a bituminous material resulting from the distillation of crude oil. Typically, asphalt is derived from the bottoms of a vacuum distillation tower and has an atmospheric boiling point of at least 380° C. Because it is hydrophobic and has good adhesiveness and weatherability, asphalt has been used widely as a binder in paving materials and as a coating for roofing shingles.
Frequently, polymeric materials have been added to asphalt to enhance its rheological properties, i.e., to improve its creep resistance above about 20° C. Polymer modified asphalts must also have good phase compatibility between the asphalt and polymer, and be storage stable at high temperatures for ease of handling and application. Compatibility between the polymer and asphalt is very important to ensure that the properties of both are transferred to the finished product for good long term performance. Poor storage stability will render the polymer modified asphalt unsuitable for use in paving binder applications, roofing applications, and other industrial specialty products. Accordingly, various methods have been suggested for maintaining storage stability.
One method requires continuous mixing of the asphalt/polymer mixture to avoid phase separation (See, for example, U.S. Pat. Nos. 4,240,946 and 4,314,921, which require high shear mixing to obtain physical dispersion of a polyolefin in bitumen. See also Transportation and Road Research Laboratory Report 1101 by J. H. Denning et. al., Highways and Structures Department, Crowthorne, Berkshire, England (1983)). Another method discloses adding one or more dispersants to a polyethylene modified asphalt to avoid phase separation (See Jew et al., Journal of Applied Polymer Science, 31, pp.2685-2704 (1986)).
In yet another method, the composition of the asphalt is tailored to ensure compatibility with the polymer used or the polymer is selected to be compatible with the asphalt (See U.S. Serial Nos. 073,813 filed June 15, 1987 and 134,954 filed Dec. 18, 1987).
In still another method, polymer modified asphalt is stabilized by the addition of an acid after the polymer has been added to the asphalt (See, for example, German patent DE 22 55 173 C3 which discloses stabilizing mixtures of asphalt and styrenic thermoplastic elastomers (styrene-butadiene-styrene) by adding small amounts of 85% o-phosphoric acid or 36% hydrochloric acid to the asphalt/SBS mixture).
However, none of these methods, alone or in combination, teach or suggest the specific method for improving the storage stability of polymer modified asphalts described hereinafter.
This invention relates to a composition and method for improving the storage stability of polymer modified asphalts. More specifically, the storage stability of an asphalt that contains greater than 1.0 wt.% of a polymer can be enhanced if the asphalt is contacted with an inorganic acid prior to adding the polymer. The resulting acid treated polymer modified product will have enhanced storage stability relative to that obtained had the acid been added with or after the polymer.
The asphalt used in this invention may be obtained from a variety of sources including straight-run vacuum residue; mixtures of vacuum residue with diluents such as vacuum tower wash oil, paraffin distillate, aromatic and naphthenic oils, and mixtures thereof; oxidized vacuum residues or oxidized mixtures of vacuum residues and diluent oils; and the like. Other asphaltic materials such as coal tar pitch, rock asphalt, and naturally occurring asphalt may also be used. Typically, the asphalt will have an atmospheric boiling point of at least 380° C., more typically of at least 440° C., and an asphaltene content of between about 5 and about 30 wt.% as determined by ASTM D4124. In paving binder applications, the asphalt will typically comprise 85, preferably 90, wt.% or more of the acid treated polymer modified product (i.e., the final product). The asphalt will typically comprise 80, preferably 85, wt.% or more of the final product when it is used in roofing applications.
An inorganic acid is then contacted with, or added to, the asphalt to form an acid treated asphalt. In general, acid addition improves the temperature susceptibility of the asphalt and the stability of the acid treated polymer modified blend. However, it is critical to obtaining a product having improved storage stability that the acid not be added to the asphalt after or with the polymer. Preferably, the inorganic acid is added slowly to the asphalt to avoid foaming which may occur if all the acid were added at one time. The inorganic acid content of the asphalt is not critical, but normally should range between about 0.2 and about 5.0 wt.%, preferably between about 0.25 and about 3.0 wt.%, of the asphalt. Although a wide variety of inorganic acids can be used, the inorganic acid will preferably be selected from the group consisting of hydrochloric acid, phosphoric acid, phosphorus pentoxide, sulfuric acid, and mixtures thereof. The term "inorganic acid" is meant to include compounds that are capable of forming an inorganic acid when contacted with the asphalt (e.g., chlorinated paraffin wax and polyvinyl chloride release hydrochloric acid when contacted with hot asphalt). Hydrochloric acid, phosphoric acid, phosphorus pentoxide, and mixtures thereof are preferred inorganic acids, with phosphoric acid being particularly preferred.
Following acid addition, the polymer is then added to the acid treated asphalt to form an acid treated polymer modified asphalt that has enhanced storage stability relative to the storage stability obtained if the polymer were added prior to or concurrent with the inorganic acid. However, the asphalt must contain greater than 1.0 wt.% (preferably at least 1.5 wt.% and more preferably at least 2.0 wt.%) of the polymer for the storage stability to be enhanced by acid addition. At polymer concentrations of 1.0 wt.% or less, polymer modified asphalts appear to be storage stable without acid addition. Conversely, polymer modified asphalts are believed to become increasingly less stable as the polymer concentration in the asphalt increases above 1.0 wt.%. However, the upper limit on the amount of polymer in the asphalt is not critical and can range up to 15 wt.% or more based on weight percent of the acid treated asphalt, although amounts below 15 wt.% are preferred. Therefore, the amount of polymer in the asphalt will typically range from above 1.0 to about 15 wt.% based on weight of the acid treated asphalt. Preferably, the amount of polymer in the asphalt will range from about 1.5 to about 15 wt.% and more preferably from about 2.0 to about 15 wt.%. When used as a paving binder, the acid treated polymer modified asphalt normally contains from about 4 to about 8 wt.% polymer. When used for roofing applications, the acid treated polymer modified asphalt normally contains from about 8 to about 15 wt.% polymer.
A wide variety of polymers may be used in this invention. Suitable polymers include both thermoplastics and thermosets, as defined by ASTM D 883-69 Standard Definitions of Terms Relating to Plastics, the disclosure of which is incorporated herein by reference. ASTM D 883-69 defines a thermoplastic as a polymer that can be repeatedly softened when heated and hardened when cooled. A thermoset is defined as a polymer that can be changed into a substantially infusible or insoluble product when cured by heat or by chemical means.
Examples of suitable thermoplastics include acetals (e.g., polymers and copolymers of formaldehyde), acrylics, acrylonitrile-butadiene-styrene plastics, cellulosics (such as cellulose acetate, propionate and acetate-butyrate), chlorinated polyethylene, fluorocarbons, nylon, polycarbonates, polyethylenes, polyphenylene oxides, polyphenylene sulfides, polypropylene, polystryene, polysulfone, polyvinyl acetates, polyvinyl alcohols, polyvinyl chlorides, polyvinylidine chloride, styrene-acrylonitrile plastics, saturated polyesters, and thermoplastic elastomers of all classes including urethanes, polyesters, styrenics and olefinics. Preferred thermoplastics are polyethylene, ethylene methacrylate, ethylene-propylene elastomer, ethylene-vinyl acetate, nylon, uncured ethylene-propylene-diene terpolymers, and uncured thermoplastic styrenic elastomers (e.g., styrene-butadiene-styrene block copolymers), with ethylene methacrylate, ethylene-vinyl acetate, or their mixtures being most preferred.
Examples of suitable thermosets include amino resins (e.g., melamine-formaldehyde, urea-formaldehyde, and mixtures thereof), phenolics, polyimides, polyuretyanes, polysulfides, silicone rubbers, unsaturated polyesters, and vulcanized (i.e., cured) rubbers (e.g., natural rubbers and cured elastomers such as ethylene-propylene-diene terpolymers and styrene-butadiene-styrene block copolymers). Preferred thermosets are polyimides, polyurethanes, and vulcanized rubbers. Most preferred are polyurethanes, cured elastomers, or their mixtures.
The particular polymers used may be readily obtained in the marketplace from various chemical suppliers. Accordingly, their methods of preparation are well known to those skilled in the art (See Encycolpedia of Polymer Science and Technology, Interscience Publishers, New York (1971); Kirk-Othmer Encyclopedia of Chemical Technology, Wiley-Interscience, 3rd Ed., New York (1981); G. L. Kinney, Engineering Properties and Applications of Plastics, John Wiley & Sons, New York (1957); and Plastics in Building, edited by Irving Skeist, Reinhold Publishing Corporation, New York (1966), the disclosures of which are incorporated herein by reference).
The conditions at which the acid and polymer are added to the asphalt are not critical and will vary with the particular asphalt and polymer used. However, the conditions will be within the ranges normally used for acid or polymer addition to asphalt. For example, acid is normally added slowly to the asphalt (typically, over a period of from about 1 to about 3 hours) at a temperature of from about 150° C. to about 250° C., preferably from about 180° C. to about 210° C. Once a substantial amount (preferably all) of the acid has been added, the acid treated asphalt is mixed for an additional period of time (typically from about 0.5 to about 1 hour, although longer times could be used because no further reaction is likely to occur once all of the acid has been reacted or depleted). The polymer is then added to the acid treated asphalt at a temperature of from about 150° to about 300° C., preferably from about 175° to about 230° C. Typically, the polymer will be added over a period of from about 1.5 to about 3 hours to ensure adequate dispersal of the polymer. Although the polymer can be added over a longer period of time, it is important not to add the polymer over too short a period because the polymer could then melt and coalesce when contacted by the hot acid treated asphalt. This would slow dispersal of the polymer in the asphalt. Once polymer addition is complete, the acid treated polymer modified asphalt is mixed for an additional 0.5 to 1.5 hours or more.
The asphalt may be mixed or blended with the acid and polymer in any number of ways that can readily be selected by one skilled in the art. Suitable means include external mixers, roll mills, internal mixers, Banbury mixers, screw extruders, augers, and the like. Normally, the mixing or blending during acid and polymer addition will be at ambient pressure.
An oxygen-containing gas (such as air) may be added to the asphalt before or during acid and polymer addition if desired. However, in a preferred embodiment of this invention, the gas is not added before or during either step because it would tend to produce asphaltenes, which would have a detrimental effect on the storage stability of the final product.
The acid treated polymer modified asphalt thus formed may be employed in essentially any application requiring asphalt-based products with superior storage stability. Examples of such applications include adhesives, coatings, fabricated products, road and roofing applications, sealants, sound and vibration dampening products, water proofing membranes and the like. However, the final product is particularly well suited for use as a paving binder, particularly a binder in the load bearing course as well as the top or surface course of hot mix pavement structures.
The present invention will be further understood by reference to the following Examples which are not intended to restrict the scope of the claims appended hereto. In the Examples, the storage stability of the acid treated polymer modified asphalts tested was measured by placing a 200 gram sample in a copper tube (10 inches high and 1 inch in diameter) and heating it to 160° C. for 5 days. Then the sample was removed from the tube and divided into top and bottom fractions. The viscosity of each fraction was measured at 135° C. and then used to calculate the ratio of the top to the bottom viscosity. A ratio of 1.0 is considered as optimum storage stability, with ratios above or below 1.0 representing mixtures that are increasingly less storage stable.
Tests were performed on several samples of a 300/400 penetration straight-run asphalt obtained from vacuum distillation. Phosphoric acid (85 wt.%) and ethylene-vinyl acetate (EVA) polymer, each alone or in combination, were added to the samples. The temperature of the samples ranged between 190° and 200° C. at all times during the tests. The order and conditions of acid and polymer addition were varied as follows:
When acid addition preceded polymer addition, the acid was added to the asphalt over approximately a twenty minute period followed by reaction with the asphalt for about an additional thirty minutes. Polymer was then added over approximately a two to three minute period and mixed with the acid modified asphalt for from about one to about two hours.
When polymer addition preceded acid addition, the polymer was added to the asphalt over from about two to about three minutes and the mixture mixed for from about one to about two hours. Acid was then added over approximately a twenty minute period followed by reaction with the polymer modified asphalt for about an additional thirty minutes.
When the acid and polymer are added together, both were added over about a five minute period and then reacted with the asphalt for an additional hour and a half.
The asphalt was stirred during acid and polymer addition. The properties of the samples tested were determined and are shown in Table 1.
TABLE 1
__________________________________________________________________________
Sample No.
1 2 3 4
Unmodified
Acid Added
Polymer Added
Acid & Polymer
Asphalt
First First Added Together
__________________________________________________________________________
Feedstock Inspections
Polymer EVA
wt. % 0 5.0
melt index, g/10 mins
-- 10
vinyl acetate, wt. %
-- 12
Asphalt, wt. %
100 94.5
Penetration at 25° C.,
318 318 318 304
mm/10
H.sub.3 PO.sub.4 (85%), wt. %
0 0.5
Product Inspections
Softening Point, °C.
31 53 52 46
Penetration at 25° C., mm/10
318 95 108 123
Viscosity at 60° C., Pa · S
34.4 373 381 166
at 135° C., cSt
171 1111 862 619
Storage Stability
1.0 1.3 2.2 4.2
__________________________________________________________________________
The data in Table 1 show that the mineral acid must be reacted with the asphalt prior to addition of the polymer (Sample No. 2) to obtain the most storage stable product. If the acid is added after or with the polymer (Sample Nos. 3 and 4), the product is less storage stable.
Example 1 was repeated using styrene-butadiene-styrene as the polymer except that when the acid and polymer were added together, both were added over about a twenty minute period followed by reaction with the asphalt for about an additional two hours. The properties of the samples tested were determined and are summarized in Table 2.
TABLE 2
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Sample No.
1 2 3 4
Unmodified
Acid Added
Polymer Added
Acid & Polymer
Asphalt
First First Added Together
__________________________________________________________________________
Feedstock Inspections
Polymer SBS
wt. % 0 5.0 5.0 5.0
molecular weight
-- 300 × 10.sup.6
wt % styrene -- 30
wt % butadiene
-- 70
Asphalt, wt. %
100 93.2
Penetration at 25° C.,
318 302 302 304
mm/10
H.sub.3 PO.sub.4 (85%), wt. %
0 1.8
Product Inspections
Softening Point, °C.
31 77 75 79
Penetration at 25° C., mm/10
318 59 68 64
Viscosity at 135° C., cSt
171 8640 3917 6317
Storage Stability
1.0 1.2 3.6 2.3
__________________________________________________________________________
The data in Table 2 confirm that the storage stability of acid stabilized polymer modified asphalts can be further enhanced if the acid is added before the polymer.
Using the procedure of Example 1, tests were performed on samples of a 150/200 straight-run asphalt. In one sample, only polymer was added. In two other samples, HCl (or Chlorez 760, a chlorinated wax available from Dover Chemical Corp.) was added before addition of ethylene-vinyl acetate. The properties of the samples tested were determined and are shown in Table 3.
TABLE 3
__________________________________________________________________________
Sample No.
1 2 3 4
Unmodified
Polymer
HCl Added
Chlorez 760
Asphalt
No Acid
First Added First
__________________________________________________________________________
Feedstock Inspections
Polymer EVA
wt. % 0 5.0
melt index, g/10 mins
-- 10
vinyl acetate, wt. %
-- 12
Asphalt, wt. %
100 95.0 91.2 93.76
Penetration at 25° C., mm/10
165 180 169 169
6N HCl, wt. % 0 0 3.8 0
Chlorez 760, wt. %
0 0 0 1.24
HCl Equivalent, wt. %
0 0 0.91 0.92
Product Inspections
Softening Point, °C.
38 55 61 61
Penetration at 25° C., mm/10
165 79 57 44
Viscosity at 60° C., Pa · S
79.5 537 1848 1951
at 135° C., cSt
254 896 1993 2066
Storage Stability
1.0 2.4 1.1 0.8
__________________________________________________________________________
The results in Table 3 show that adding hydrochloric acid or compounds that form hydrochloric acid (e.g., Chlorez 760) to the asphalt before the polymer produces a product having enhanced storage stability relative to that obtained if no acid were added.
Using the procedure of Example 1, linear low density polyethylene, alone or after hydrochloric acid or Chlorez 760, was added to samples of a 100/200 penetration straight-run asphalt. The properties of the samples tested were determined and are shown in Table 4.
TABLE 4
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Sample No.
1 2 3
Polymer
HCl Chlorez 760
No Acid
Added First
Added First
______________________________________
Feedstock Inspections
Polymer Linear Low Density Polyethylene
wt. % 5
melt index, g/10 mins
20
density, g/cm.sup.3
0.924
Asphalt, wt. %
95 93.76 88.2
Penetration at 25° C.,
160 158 168
mm/10
6N HCl, wt. % 0 0 6.8
Chlorez 760, wt. %
0 1.24 0
HCl Equivalent, wt. %
0 0.92 1.64
Product Inspections
Softening Point, °C.
49 57 61
Penetration at 25° C.,
97 55 43
mm/10
Viscosity at 60° C.,
3338 2207 3779
Pa · S
at 135° C., cSt
786 1989 2651
Storage Stability
(1) 2.3 3.1
______________________________________
(1) Viscosity of top phase too high to measure.
The results in Table 4 show that the addition of hydrochloric acid or Chlorez 760 (which produces HCl at the blending conditions) to the asphalt before polyethylene addition forms a product having enhanced storage stability relative to that obtained if no acid were added.
Using the procedure of Example 1, Chlorez 760 and a different grade of ethylene-vinyl acetate were added to samples of a 100/200 penetration straight-run asphalt, the Chlorez 760 being added before the polymer. The properties of the samples tested were then determined and the results shown in Table 5.
TABLE 5
______________________________________
Sample No.
1 2
Polymer
Chlorez 760
No Acid
Added First
______________________________________
Feedstock Inspections
Polymer EVA EVA
wt. % 5 5
melt index, g/10 mins.
3 3
vinyl acetate, wt. %
9 9
Asphalt, wt. % 95 93.76
Penetration at 25° C., mm/10
190 168
Chlorez 760, wt. % 0 1.24
HCl Equivalent, wt. %
0 0.92
Product Inspections
Softening Point, °C.
47 61
Penetration at 25° C., mm/10
99 60
Viscosity at 60° C., Pa · S
(1) 3511
at 135° C., cSt
997 2335
Storage Stability 4.9 1.4
______________________________________
(1) Too high to measure.
The results in Table 5 show that an asphalt modified with other grades of EVA also has improved storage stability provided the asphalt has first been reacted with a mineral acid (HCl from degradation of the chlorinated wax at the blending temperature).
Using the procedure of Example 1, hydrochloric acid (or Chlorez 760) and the ethylene-vinyl acetate of Example 1 were added to samples of a 100/200 penetration straight-run asphalt, with the acid (or Chlorez 760) being added first. The properties of the samples tested were then determined and the results shown in Table 6.
TABLE 6
__________________________________________________________________________
Sample No.
1 2 3 4 5
Chlorez 760
HCl Chlorez 760
HCl Chlorez 760
Added First
Added First
Added First
Added First
Added First
__________________________________________________________________________
Feedstock Inspections
Polymer EVA
wt. % 5
melt index, g/10 mins.
10
vinyl acetate, wt. %
12
Asphalt, wt. %
94.8 94.0 94.5 91.2 93.76
Penetration at 25° C.,
168
mm/10
Chlorez 760 wt. %
0.2 0 0.5 0 1.24
6N HCl, wt. % 0 1.0 0 3.8 0
HCl Equivalent, wt. %
0.15 0.24 0.37 0.91 0.92
Product Inspections
Softening Point, °C.
54 55 57 61 61
Penetration at 25° C., mm/10
66 63 60 57 44
Viscosity at 60° C., Pa · S
698 794 1090 1848 1951
at 135° C., cSt
1321 1464 1589 1993 2066
Storage Stability
2.0 1.8 1.7 1.1 0.8
__________________________________________________________________________
The results in Table 6 show that as the percent of acid reacted with the asphalt is increased (on an equivalent HCl basis), the storage stability is improved.
Example 1 was repeated at different concentrations of phosphoric acid and ethylene-vinyl acetate in which the acid was added to the asphalt before the polymer. The results obtained are shown in Table 7.
TABLE 7
__________________________________________________________________________
Sample No.
1 2 3 4 5 6
__________________________________________________________________________
Feedstock Inspections
Polymer EVA
wt. % 0.5 0.5 1.0 1.0 2.0 2.0
melt index, g/10 mins
10
vinyl acetate, wt. %
12
Asphalt, wt. %
99.5
99 99 98.5 98 97.5
Penetration at 25° C.,
309
mm/10
H.sub.3 PO.sub.4 (85%), wt. %
-- 0.5 -- 0.5 -- 0.5
Product Inspections
Softening Point, °C.
34 40 33 38 38 48
Penetration at 25° C., mm/10
288 188 271 182 216 115
Viscosity at 60° C., Pa · S
40 82 44 91 74 209
at 135° C., cSt
195 294 220 324 321 648
Storage Stability
1.0 1.0 1.2 (1)
1.2 (1)
1.9 1.2
__________________________________________________________________________
(1) An average of three measurements.
The data in Table 7 show that the storage stability of a polymer modified asphalt is not enhanced by acid addition at polymer concentrations of 1.0 wt.% or less. The data also show that at polymer concentrations greater than 1.0 wt.%, acid addition prior to polymer addition enhances the storage stability of polymer modified asphalts.
Claims (27)
1. A method for improving the storage stability of an asphalt that contains from above 1.0 to about 15 wt.% of a polymer which comprises
(a) adding from about 0.2 to about 5 wt.% of an inorganic acid to the asphalt to form an acid treated asphalt, and thereafter,
(b) adding the polymer to the acid treated asphalt to form an acid treated polymer modified asphalt which has a greater storage stability than that obtained had the acid been added with or after the polymer.
2. The method of claim 1 wherein the acid is selected from the group consisting of hydrochloric acid, phosphoric acid, phosphorus pentoxide, sulfuric acid, and mixtures thereof.
3. The method of claim 2 wherein the acid is selected form the group consisting of hydrochloric acid, phosphoric acid, and mixtures thereof.
4. The method of claim 1 wherein from about 0.25 to about 3 wt.% of the acid is added to the asphalt.
5. The method of claim 4 wherein from about 1.5 to about 15 wt.% of the polymer is present in the acid treated asphalt.
6. The method of claim 5 wherein the polymer is a thermoplastic polymer, a thermoset polymer, or their mixtures.
7. The method of claim 6 wherein the thermo-plastic polymer is polyethylene, ethylene methacrylate, ethylene-propylene elastomer, ethylene-vinyl acetate, nylon, uncured ethylene-propylene-diene terpolymers, uncured thermoplastic styrenic elastomers, or mixtures thereof.
8. The method of claim 6 wherein the thermoset polymer is polyimides, polyurethanes, vulcanized rubber, or mixtures thereof.
9. The method of claim 1 where from about 1.5 to about 15 wt.% of the polymer is present in the asphalt.
10. A method for improving the storage stability of an asphalt containing from above 1.0 to about 15 wt.% of a thermoplastic polymer, a thermoset polymer, or mixtures thereof, which comprises
(a) adding from about 0.2 to about 5 wt.% of an inorganic acid selected from the group consisting of hydrochloric acid, phosphoric acid, phosphorous pentoxide, sulfuric acid, and mixtures thereof to the asphalt to form an acid treated asphalt, and
(b) adding the polymer to the acid treated asphalt to form an acid treated polymer modified asphalt that has greater storage stability than that obtained had the acid been added with or after the polymer.
11. The method of claim 10 wherein the acid is hydrochloric acid, phosphoric acid, or their mixtures.
12. The method of claim 11 wherein the acid comprises phosphoric acid.
13. The method of claim 11 wherein the thermoplastic polymer is ethylene methacrylate, ethylene-vinyl acetate, or their mixtures.
14. The method of claim 13 wherein the thermoset polymer is polyurethanes, cured elastomers, or their mixtures.
15. The method of claim 10 wherein the acid treated polymer modified asphalt contains at least 80 wt.% asphalt and from about 8 to about 15 wt.% polymer.
16. The method of claim 10 wherein the acid treated polymer modified asphalt contains at least 85 wt.% asphalt and from about 4 to about 8 wt.% polymer.
17. The method of claim 10 wherein the thermoplastic polymer is polyethylene, ethylene methacrylate, ethylene-propylene elastomer, ethylene-vinyl acetate, nylon, uncured ethylene-propylene-diene terpolymers, uncured thermoplastic styrenic elastomers, or mixtures thereof.
18. The method of claim 10 wherein the thermoset polymer is polyimides, polyurethanes, vulcanized rubber, or mixtures thereof.
19. The method of claim 10 wherein from about 1.5 to about 15 wt.% of the polymer is present in the acid treated asphalt.
20. A method for improving the storage stability of an asphalt containing from above 1.0 to about 15 wt.% of a thermoplastic polymer, a thermoset polymer, or mixtures thereof, which comprises
(a) adding from about 0.2 to about 5 wt.% of an inorganic acid selected from the group consisting of hydrochloric acid, phosphoric acid, and mixtures thereof to the asphalt to form an acid treated asphalt, and
(b) adding the polymer to the acid treated asphalt to form an acid treated polymer modified asphalt that has greater storage stability then that obtained had the acid been added with or after the polymer,
wherein the thermoplastic polymer is ethylene methacrylate, ethylene-vinyl acetate, or their mixtures; the thermoset polymer is polyurethanes, cured elastomers, or their mixtures; and the acid treated polymer modified asphalt contains at least 80 wt.% asphalt.
21. The method of claim 20 wherein the acid comprises phosphoric acid.
22. The method of claim 21 wherein from about 0.25 to about 3 wt.% of the acid is added to the asphalt.
23. The method of claim 21 wherein the acid treated polymer modified asphalt contains from about 8 to about 15 wt.% polymer.
24. The method of claim 21 wherein the acid treated polymer modified asphalt contains at least 85 wt.% asphalt and from about 4 to about 8 wt.% polymer.
25. The method of claim 21 wherein the thermoplastic polymer is ethylene-vinyl acetate.
26. The method of claim 20 wherein from about 1.5 to about 15 wt.% of the polymer is present in the acid treated asphalt.
27. The method of claim 21 wherein from about 2 to about 15 wt.% of the polymer is present in the acid treated asphalt.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/397,215 US5070123A (en) | 1988-08-29 | 1989-08-23 | Method for improving the storage stability of polymer modified asphalt |
| US07/517,776 US5095055A (en) | 1989-08-23 | 1990-05-02 | Using branched polymers to improve the storage stability of acid treated polymer modified asphalts (PNE-577) |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US23702888A | 1988-08-29 | 1988-08-29 | |
| US07/397,215 US5070123A (en) | 1988-08-29 | 1989-08-23 | Method for improving the storage stability of polymer modified asphalt |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US23702888A Continuation-In-Part | 1988-08-29 | 1988-08-29 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/517,776 Continuation-In-Part US5095055A (en) | 1989-08-23 | 1990-05-02 | Using branched polymers to improve the storage stability of acid treated polymer modified asphalts (PNE-577) |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US5070123A true US5070123A (en) | 1991-12-03 |
Family
ID=26930332
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/397,215 Expired - Lifetime US5070123A (en) | 1988-08-29 | 1989-08-23 | Method for improving the storage stability of polymer modified asphalt |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US5070123A (en) |
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| US5248407A (en) * | 1992-07-16 | 1993-09-28 | Exxon Research And Engineering Company | Storage stable polymer modified asphalt paving binder |
| US5252641A (en) * | 1990-02-21 | 1993-10-12 | Institut Francais Du Petrole | Process for production of bituminous compositions containing polymeric residues |
| US5288773A (en) * | 1992-03-05 | 1994-02-22 | Exxon Research And Engineering Company | Sulfonated unhydrogenated copolymers of styrene and butadiene |
| US5308898A (en) * | 1990-02-21 | 1994-05-03 | Institut Francais Du Petrole | Bituminous compositions including residues of thermoplastic polymers with polyurethane foams and thermoset resin, etc. |
| US5328943A (en) * | 1991-07-24 | 1994-07-12 | Nippon Oil Co., Ltd. | Asphalt compositions for pavement |
| WO1995025136A1 (en) * | 1992-03-05 | 1995-09-21 | Exxon Research And Engineering Co. | Sulfonated unhydrogenated copolymers of styrene and butadiene |
| US5455291A (en) * | 1994-02-14 | 1995-10-03 | U.S. Intec, Inc. | Coal-tar-pitch-based compositions |
| FR2718747A1 (en) * | 1994-04-18 | 1995-10-20 | Elf Antar France | Process for the preparation of bitumen / polymer compositions of reinforced multigrade nature and application of the compositions obtained to the production of bitumen / polymer binders for coatings. |
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